Anthraquinone vat dyestuffs



Patented Dec. 25, 1951 THRAQUINONE VAT DYE STUFFS Paul Sutter,Binningen, and Walter Kern, Sissach, Switzerland, assignors to CibaLimited, Basel,

Switzerland, a Swiss firm No Drawing. Application June .23, 1949, SerialNo. 100,964. In Switzerland July 9, 1948 Claims; (01. 260-261) 1 It isknown that certain quinazoline derivatives are valuable intermediateproducts for the manufacture of vat dyestuffs (see French Patents Nos.822,194 and 822,428). However, these quinazolines have been madehitherto by a complicated process and, furthermore, some of the startingmaterials are difficult to obtain.

Application Serial No. 756,808, filed June 24,

1947,.(now' U. s. Patent No. 2,530,025, granted, November 14', 1950),describes a simpler process a for making these in part known quinazolinederivatives'fw-l'iich consists in treating acylamino aryl-ortho-nitrileswith agents capable of replacing a hydroxyl group by halogen. As suchagents there come into consideration known substances which are capable,for example, of converting an acid into the corresponding acid halide.The use oi phosphorus pentachloride is especially advan- It is-an objectof the present invention to-provide new diquinazoline' compounds and vatdyes'tufis containing a new diquin'azoline configuration. Furtherobjects will appear as the specification proceeds. a

According to the present invention valuable, quinazolines are madebytreating withan'agent capable of bringin about ring closure anacylamino-anthraquinone, in which two aminoanthraquinone residues areconnected together by the residue of a dicarboxylic acid containing atleast one aromatic nucleus and of which the carboxyl groups arearomatically bound, and in which each "anthraquinone residue containsorth'o-position to the acylamind'group a. group containing the atomicgrouping -C N--'-.

acids which may contain up to four rings fluoranthene ,dicarboxylic acidterphenyl-4:4-di-. carboxylic acid and especiallydiphenyl-4:4'-dicarboxylic acid. A useful dicarboxylic acid containing aheteroatomic ring besides two aromatic rings is, for example,diphenylene oxide-3:6-dicarboxylic acid.

The agents capable of bringing about ring closure are advantageouslychosen in accordance The starting'materials required far the'presentprocess can be obtained, for example, from amino-.

anthraquinones, especially 2-aminoanthraquinones, which contain inortho-position to the amino group, especially in the 3-position, a groupcontaining the atomic grouping C N--, for example, a cyano group or anacid amide group. As theresidue of the dicarboxylic acid, which con-.nects together the two aminoanthraquinone -residues; there-comes intoconsideration-,ior example, the residue of a purely aromaticdicarboxylic acid, that is to say one which is free from heterocyclic orhydrogenated rings, andespecially a polynuclear aromatic dicarboxylic'acid; and also the residue of an' aromatic dicarboxylic acid whichcontains a'heterocy'clic ring. As examples oi purely aromaticdicarboxylic acids theremay be mentioned as mononuclear acids'is'o'phthalic acid and -terephthalic' "acid' and as izaolv nuelear withthe starting material to be used. Thus, for example; in the case ofthose acylaminoanthraquinone's which still contain an acid amide groupin ortho-position to the acylamino group it is of advantage in somecases to use alkaline condensing agents for bringing about ring closure,and in the case of cyano-acylamino-anthraquinones phosphoruspentachloride may be used with advantage. 7

Thus, for example, a useful starting material for the present process isobtained bycondensing 2 mols of 2-amino-3-cyanoanthraquinone withcliphenyl-4:4'-dicarboxylic acid chloride, which product upon treatmentwith phosphorus pentachloride in nitrobenzene yields directly adiquinazoline containing chlorine as a substituent in the 4'-position ofeach quinazoline residue. The resulting product is a valuableintermediate product for the manufacture of dyestuffs.

The invention also includes a process for making new vat dyestuffs, inwhich a diquinazoline containing halogen as a substituent in the 4-posi-,tion of each quinazoline residue, and obtainable by the process abovedescribed, is reacted with an amine containing at least one replaceablehydrogen atom in the amine group. There are used with advantage primaryamines of the aliphatic,

- hydroaromatic, aromatic or heterocyclic series,

7 color and fastness are not'easily obtainable with such as methylamine,ethylamine, aminoben- 3 other components. Thel-amino-anthraquinone-acridones, such, for example, as4-aminoanthraquinone-benzacridones, may, if desired, contain furthersubstituents, such as usually occur in vat dyestuffs, for example,halogen atoms,

in the Bz-nucleus.

Examples of such substituted 4-amino-anthraquinone-benzacridones are theproducts containing the following substituents in the positions as shownin the formula N da:

2': 3' :5.-trichloro, l'etrifiuormethyl, l'-trifiuormethyl-6-chloro,4'-methyl or methoxy. The substituents should of source be ofnon-ionogenic character and preferably of an atomic or radicalic weightvnot exceeding 80. 7

As, a general rule the influence of such substituents is not very markedand a beneficial IQSult brought about thereby, if any, is so small,

the boiling point of the solvent. It is also possible to use an excessof the amine as a solvent.

The intermediate products and vat dyestuffs obtainable in accordancewith the invention are new. The vat dyestufifs can be used in knownmanner for dyeing or printing a very wide variety of materials, such aswool or silk, and especially for dyeing or printing cellulosicfibresSuch as cotton or artificial silk or staple fibres of regeneratedcellulose. They can also be converted by known methods into salts ofsulphuric acid leuco esters and similar compounds and used by themethods usual for, this class. of dyestuffs.

The following examples illustrate the invention, the parts andpercentages being by weight unless otherwise stated and the relationshipof parts by weight to parts by volume being the same as that of thekilogram to the litre:

N NC obtained by condensing z-amino-s-cyano-am thraquinone withdiphenyl-4:4' -dicarb0xylic acid chloride, are heated at the boil with4.8 parts of is obtained in: the 'form of a sparingly solublecrystalline powder. V 2.5 parts "of the latter diquinazoline are heatedat the boil with 2.3 .partsiof 4-amino-anthraquinone-2:1.(N)-.benzacridone in 50. parts of phenol for, hour. There are. then added50. parts of anhydrous pyridine, the wholeis'allowedto cool to about 6 0C., and the. product is separated by filtering- {with suction, washedwith benzene and dried. C

The r q rm ct may be purified in the f lw n meeaer It. s de a ted.i1}..a l. t1:1 hilt times: its .wei'ghtof; sulphuric acid of about 90 ercent strength, and slowly dilutedwith sulphuric acid of about 70 percent strength until the concentration of te sulphuric acid has fallen toabout '72 per cent and the dyestufi has precipitated in the form of abrown crystalline sulphate. After cooling, the product is separated byfiltering with.

suction, and the sulphate is decomposed with water, separated byfiltration, washed with water,

and dried. There is obtained a green powder of the formula which dyescotton trom: .avi'olet-brown vat fast yellow-green tints If in thisexample 2.5 parts of 4-amino-anthraquinone-2 1 (N) -1' :2 (N)-5'-chloro-benzacridone are substituted for the 2.3 parts of4-aminoanthraquinone-2: 1 (N) -benzacridone,. a very similar dyestuff isobtained. An asymmetrical dyestuff consisting mainly of. the compound ofthe formula of very similar properties is obtained if 2.5 parts of thediquinazoline are first heatedto about 120 C. with 1.25 parts of4-amino-anthraquinone-2:1(N) -1': 2'(N) 5'- chloro benzacridone for /2hour, then after addition of 1.15 parts of fi-amino anthraquinone 2:1(N)--benzacridone the whole is heated to the boil for another hour.

7 Example 2 which dyes cotton from a brown-violet vat yel- 1 part of theacid amide of the formula low-green tints- II NHOC O V V g L (obtainablefrom fluoranthene dicarboxylic acid Example 3 dichloride and2-amino-3-cyano-anthraquinone; 2 parts of the acid amide of the formulthe fluoranthene,dicarboxylic acid can be made 0 o fromdibromo-fiuoranthene by reaction with II II cuprous cyanide andhydrolysis of the resulting NHQC CONH dinitrile in the manner describedin Patent No. 2,292,691) and 0.7 part of phosphorus penta- CN NCchloride are heated at the boil in 60 parts of nitrobenzene for /2 hour.After cooling, the prodnot is separated by filtering with suction,washed (obtainable from 2-amino-3-cyano-anthraqulwith nitrobenzene, andthen with benzene, and none and iso-phthalic acid dichloride) are heateddried. There is obtained a yellow-red powder at the boil with 2.4 partsof phosphorus pentacorresponding to the formula chloride in 60 parts ofanhydrous nitrobenzene t 0 ll N\ N c 0.5 part of the latter quinazolinederivative is for /z hour. After cooling, the product is sepaheated atthe boil with 04 part of rated by filtration, Washed with nitrobenzeneand then with benzene and dried. There is obtained n 12 ;23 :322 ig ggigg pfi g g gz a yellowish powder corresponding to the formula then added,the whole is allowed to cool to o 0 approximately 60 C., and the Productis sepa- 40 H l a rated by filtering with suction. The filter residue 0-(f is washed with alcohol and dried. /ILI N\ For the purposes ofpurification the product is 4* E Z dissolved in about 100 parts ofsulphuric acid of 95 per cent strength 35 parts of Sulphunc acid 4 partsof the latter quinazoline derivative are f p r centst n t are graduallyd heated at the boil with 3.7 parts of 4-aminoand t brown crystallinesulphuric acid salt of m anthraquinone2:1(N)-benzacridone in 70 parts ofphenol for hour. The whole is allowed to the dyestufi is separated byfiltering with succool to approximately C" parts of pyridine tion. Afterdecomposing the latter with water, it are added, and the product isseparated by filteris separated by filtration, and thoroughly washed ingwhile hot. 'The filter residue is washed with alcohol and dried. withwater and dried. There is obtained the The product may be purified byfractional dyestuff of the formula precipitation from sulphuric acid inthe manner 19. described. in; Example.: :2. The; dyestuff so ob.-tained. has? the-wformula.

and dyes cotton from a brown-violet vat yellowreen tints.

Example 4 a parts of the acid amide of the formula (obtainable fromdiphenylene oxide-3:6-dicarboxylic acid chloride and.2.-amino-3-cyanoanthraquinone) and. 5.6 parts of phosphoruspentachloride areheated'atithe boil in 240 parts of nitrobenzene' for Lhour: After cooling, the product is separated by filtering with.suction;

washed with nitrobenzene and thenwith benzene and dried There isobtained a\yellow -red product corresponding to the formula 1.0.,4:5?parts:-of;thelatter quinazoli'ne derivative are heated: at the boilwith: 3;6 partsof 4-aminoanthraquinone 2 l- (N) -'benzacridone in 80-parts of phenol for hour: 80 partso'f'pyridine are,

6- then added, thewhole is allowed .to cool'to approximately 60 C., andtheproducti'Sseparated by filtering with suction. Th'efilter,residuel-is washed with alcohol-and dried;

For thepurpose of purification the product is dissolved in the necessaryquantity of sulphuric acid"of 98 per cent. strength, the whole: isgradually; diluted with water until' the sulphuric acid hasaconcentration of '72 per cent., and the pre- 15 cipitated brown sulphateis separatedby/filtering with suction. After decomposition with water,the product is separated by filtration, washed with water and dried. Thed'yestufi so obtained 2g is of the formula and dyes cotton from abrown-violet vat yellowgreen tints.

Example 5 4.. 7 2 parts of the dyestufi obtained as described in thethird paragraph of Example 1 are vatted at 50 C. in 300 parts of waterwith the addition of 8 parts by volume of caustic soda solution of 36 0'B. and 4 parts of sodium hydrosulphite. A dyebath is prepared from 2700parts of water, 7 parts by volume of caustic soda solution of 36 B. and4 parts of sodium hydrosulphite and the stock vat above described isadded 100 parts of wetted cotton are entered into the dyebath at 40 C.,and after 15 minutes 60 parts of sodium chloride are added and dyeing iscarried on for '11 lihourv while raising the temperature to 50C. Thecotton is then squeezed, oxidised in the air, rinsed, acidified, againrinsed and soaped at the boil for hour with a solution containing, perlitre of water, 3 grams of soap and 1 gram of anhydrous sodiumcarbonate. The cotton is dyed a fast yellow green tint.

What we claim is: 1. A vat dyestuff of the formula wherein R stands foran aromatic radical free from hydrogenated and heterocyclic rings andcontaining up to four rings and bound directly by two ring carbon atomsto the quinazoline radicals, and wherein each of R1 and'R stands for aradical of 1 an -anthraquin0ne'-2:'i(N) l acridone attached in its iposition to the'res'pective --NH-groups shown in the formula.

2. A vat dyestufi of the formula n Rz-NH I n l N C-R-A!) 10. 15 \N o r'mV l I. wherein R stands for a radical of the formula wherein n is aninteger ndtgreater than 3 and Col-I4 represents a phenylene radical, andwherein each of R1 and R2 stands for a radical of ananthraquinone-2:1(N)-acridone attached in its i-position to therespective -1NHgroups shown in the formula.

3. The vat dyestuff of the formula 4. The vat dyestufi of the formulaPAUL SU'I'IER.

WALTER KERN.

14 REFERENCES CITED The following references are of record in the fileof this patent:

UNITED STATES PATENTS Number Name Date 2,187,813 Baumann et a1 Jan. 23,1940

1. A VAT DYESTUFF OF THE FORMULA